CN109715690A - Resin combination and the thermal conductivity soft sheet material and radiator structure for using the resin combination - Google Patents

Resin combination and the thermal conductivity soft sheet material and radiator structure for using the resin combination Download PDF

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Publication number
CN109715690A
CN109715690A CN201780055101.0A CN201780055101A CN109715690A CN 109715690 A CN109715690 A CN 109715690A CN 201780055101 A CN201780055101 A CN 201780055101A CN 109715690 A CN109715690 A CN 109715690A
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thermal conductivity
resin combination
sheet material
soft sheet
compound
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CN201780055101.0A
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CN109715690B (en
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吉本光彦
下山卓宏
饭塚真实
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Nisshinbo Holdings Inc
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Nisshinbo Holdings Inc
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V29/00—Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
    • F21V29/50—Cooling arrangements
    • F21V29/502—Cooling arrangements characterised by the adaptation for cooling of specific components
    • F21V29/503—Cooling arrangements characterised by the adaptation for cooling of specific components of light sources
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F2013/001—Particular heat conductive materials, e.g. superconductive elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2255/00—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
    • F28F2255/02—Flexible elements
    • H—ELECTRICITY
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body

Abstract

It is non-silicon class material that the present invention, which provides a kind of, excellent flexibility, and the thermal conductivity soft sheet material of the superior in durability such as heat-resistant aging, humidity resistance and thermal shock resistance, and the radiator structure using the thermal conductivity soft sheet material, in addition, operability is excellent in kneading process when providing heat conductive sheet preparation, is suitable as the resin combination of the adhesive material of thermal conductivity soft sheet material.The present invention relates to resin combinations, include thermal conductivity soft sheet material made of the resin combination and the solidification of the blend compositions of thermal conductivity inorganic filler, and the radiator structure using the thermal conductivity soft sheet material, the resin combination includes block urethane prepolymer, defined epoxide and curing catalysts, the block urethane prepolymer is in the reaction product of hydrogenated butadiene polymer class polyalcohol that aliphatic diisocyanate compound and two ends have hydroxyl, the reaction product is formed in the isocyanate group that end has by aromatic hydroxy compound block.

Description

Resin combination and thermal conductivity soft sheet material and the heat dissipation for using the resin combination Structure
Technical field
The present invention relates to the resin combination for the adhesive for being suitable as thermal conductivity soft sheet material, use the resin combination Thermal conductivity soft sheet material and radiator structure.
Background technique
The electronic components such as LED or CPU used in Electrical connections, power supply IC, can be adjoint when these devices use A large amount of fevers.Such generate heat both had interfered the normal operating of Electrical connections, and then was also possible to lead to failure or breakage.Cause This is escaped the heat generated from the heaters such as electronic component as described so using the radiator of heat sink or metal framework etc. It is dissipated to outside.
At this point, clamping the insulating material by high-termal conductivity between heater and radiator to improve heat dissipation effect The sheet material of composition efficiently carries out the heat transfer from heater to radiator.Such sheet material is commonly referred to as fin material or leads Hot sheet material etc..
Heat conductive sheet is generally using conducting filler as principal component, using the adhesives such as resin or rubber as accessory ingredient It constitutes.Heat conductive sheet naturally needs to pursue thermal conductivity and insulating properties, in addition to this, also pursue in order to obtain heater with Flexibility needed for radiator good adhesion can be required after long-term heat resistance (heat-resistant aging), wet-heat resisting in turn The endurance qualities such as property and thermal shock resistance (cold-hot cycle characteristics).
From this point of view, as adhesive, silicon rubber or silicone resin were widely used in the past (for example, referring to patent Document 1).
In addition, being proposed using soft epoxy resin (patent document 2) or polyurethanes (specially as non-silicon class material Sharp document 3) etc. sheet material.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-80617 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2012-251089 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2009-13237 bulletin
Summary of the invention
However, when using the silicon class material of silicon rubber or silicone resin etc. as adhesive, although available on 150 DEG C of left sides The heat conductive sheet of excellent heat resistance at a high temperature of the right side, however the low molecular weight polyorganosiloxane due to containing in the silicon class material volatilizees, It is attached to the contact portions of electric device and decomposition, can lead to the problem of and cause contact obstacle or poor flow.
In contrast, when used as the epoxy resin or polyurethanes of non-silicon class material as adhesive, although The above-mentioned low molecular weight polyorganosiloxane by silicon class material such as, which will not be led to the problem of, to be caused, however the SC service ceiling temperature of heat conductive sheet Only up to 130 DEG C, the heat resistance of such as silicon class material cannot be obtained.It is especially difficult to attain full and complete satisfaction in heat-resistant aging The requirement of aspect.
In addition, epoxy resin easily causes curing reaction at low temperature since the reactivity of epoxy group is high.Cause This, there is also following problems, that is, when by as the conducting filler of principal component with high concentration dispersion, filling, due in original In the kneading process of material heating reduce viscosity, and be difficult to ensure proper viscosity heat conductive sheet preparation when the problem of.
Therefore, the adhesive used as heat conductive sheet seeks not siliceous class material, and can obtain flexibility, heat-resisting The material of the heat conductive sheet of the superior in durability of aging, humidity resistance and thermal shock resistance etc..In addition, also seeking thermally conductive Property sheet material preparation when kneading process in the excellent material of operability.
In order to solve the above-mentioned technical problem the present invention obtains, its purpose is to provide a kind of non-silicon class materials, for softness Property is excellent, and the thermal conductivity soft sheet material of the superior in durability of heat-resistant aging, humidity resistance and thermal shock resistance etc., and The radiator structure of the sheet material is used.
In addition, the purpose of the present invention lie also in provide heat conductive sheet preparation when kneading process in operability it is excellent It is good, the resin combination of the adhesive material of thermal conductivity soft sheet material can be suitable as.
It is completed the present invention is based on following discoveries: comprising defined block urethane prepolymer, defined epoxidation The resin combination for closing object and curing catalysts, can be used as the adhesive material of thermal conductivity soft sheet material, in operability and solidification It is suitable in terms of the characteristic of object.
That is, the present invention provides following [1]-[11] item.
[1] a kind of resin combination comprising block urethane prepolymer, epoxide and curing catalysts, The block urethane prepolymer is the poly- fourth of hydrogenation for having hydroxyl in aliphatic diisocyanate compound and two ends In the reaction product of dienes polyalcohol, the reaction product is passed through into aromatic hydroxy in the isocyanate group that end has It closes object block to form, the structural unit from the aliphatic diisocyanate compound in the reaction product, relative to next It is 1.6-2.8 moles from 1 mole of structural unit of the hydrogenated butadiene polymer class polyalcohol, the epoxide has 2-6 A epoxy group, relative to 1 mole of hydroxyl of the aromatic hydroxy compound, the epoxy group is 0.9-2.5 moles.
[2] resin combination as described in above-mentioned [1], wherein the molecular weight of the epoxide less than 600, and Epoxide equivalent is less than 200g/eq.
[3] resin combination as described in above-mentioned [1] or [2], wherein the number of the hydrogenated butadiene polymer class polyalcohol is equal Molecular weight is 800-5000.
[4] resin combination as described in any one of above-mentioned [1]-[3], wherein the aromatic hydroxy compound For resorcinol.
[5] resin combination as described in any one of above-mentioned [1]-[4], wherein the curing catalysts are quaternary ammonium Salt.
[6] a kind of preparation method of resin combination, for the resin combination as described in any one of above-mentioned [1]-[5] The preparation method of object, this method include following process: making the aliphatic two different in the presence of urethanation catalyst Cyanate esters and the hydrogenated butadiene polymer class polyol reaction obtain reaction product of the end with isocyanate group Process；The aromatic hydroxy compound is added in the reaction product, carries out the blocked reaction of the isocyanate group, The process for obtaining the block urethane prepolymer；And it is at least blended in the block urethane prepolymer The epoxide and the curing catalysts, the process for obtaining the resin combination.
[7] preparation method of the resin combination as described in above-mentioned [6], wherein obtaining the block urethane In the process of prepolymer, by the aromatic hydroxy compound with the isocyanide relative to the aliphatic diisocyanate compound The hydroxyl of 1 mole of aromatic hydroxy compound of perester radical is that 0.9-1.1 moles of mode is added.
[8] a kind of thermal conductivity soft sheet material is made comprising resin combination described in any one of above-mentioned [1]-[5] Resin sheet made of blend compositions solidification with thermal conductivity inorganic filler, the thermal conductivity soft sheet material is according to JIS K7312: The hardness of 1996 c-type determination of hardness test is 95 or less.
[9] as above-mentioned [8] record thermal conductivity soft sheet material, wherein the thermal conductivity inorganic filler aluminium chelate compound into Row surface treatment.
[10] a kind of preparation method of thermal conductivity soft sheet material, the thermal conductivity soft sheet material recorded for above-mentioned [8] or [9] Preparation method, this method includes following process: the resin combination is at least mixed with the thermal conductivity inorganic filler, adjust The process for making the blend compositions；It mediates, roll the blend compositions, the process for obtaining uncured predecessor；And By the way that the presoma is pressurizeed at 120-250 DEG C and makes its solidification, the process for obtaining the thermal conductivity soft sheet material.
[11] a kind of radiator structure is soft with the thermal conductivity of heater and radiator clamping above-mentioned [8] or [9] record Sheet material.
The operability of resin combination of the invention in the kneading process when prepared by heat conductive sheet is excellent, can be suitble to use Make the adhesive material of thermal conductivity soft sheet material.
In addition, adhesive is by non-silicon class material structure using the thermal conductivity soft sheet material of the invention of the resin combination At with excellent flexibility, and the endurance quality of heat-resistant aging, humidity resistance and thermal shock resistance etc. is also excellent.Therefore, By using the thermal conductivity soft sheet material, contact obstacle or the generation of poor flow of electric device, energy not will lead to Access excellent radiator structure.
Specific embodiment
Hereinafter, to resin combination and preparation method thereof of the invention, the thermal conductivity using the resin combination is soft Sheet material and preparation method thereof, and be described in detail using the radiator structure of the thermal conductivity soft sheet material.
[resin combination]
Resin combination of the invention includes block urethane prepolymer, epoxide and curing catalysts.Institute Stating block urethane prepolymer is the hydrogenation polybutadiene for having hydroxyl in aliphatic diisocyanate compound and two ends In the reaction product of alkenes polyalcohol, the reaction product is passed through into aromatic hydroxy compound in the isocyanate group that end has Object block forms, the structural unit from the aliphatic diisocyanate compound in the reaction product, relative to coming from 1 mole of structural unit of hydrogenated butadiene polymer class polyalcohol is 1.6-2.8 moles.In addition, the feature of the epoxide exists In with 2-6 epoxy group, relative to 1 mole of hydroxyl of the aromatic hydroxy compound, the epoxy group is 0.9-2.5 Mole.
The resin combination does not solidify, with thermal conductivity in heat conductive sheet preparation at 100 DEG C of temperature below Filler mixing can be mediated with viscosity appropriate, in addition, can keep such viscosity at least 6 hours.Therefore, make conducting filler On the basis of equably filling, dispersing, sufficient kneading time, the operability in kneading process can be also ensured with viscosity appropriate It is excellent.
(solidfied material of resin combination)
The solidfied material of resin combination of the invention, as be described hereinafter, by the way that the resin combination is heated to 120 DEG C or more, Curing reaction is carried out, solidfied material is generated.
Solidfied material has the gel network structure being mainly made of 2 kinds of cross-linking polymerizations.
First cross-linking polymerization is reacting for hydrogenated butadiene polymer class polyalcohol and aliphatic diisocyanate compound The end of product, taken off by the isocyanate group of aromatic hydroxy compound block it is blocked, by dimerization generate urea diketone, Or it is reacted by the multimerization that trimerizing generates chlorinated isocyanurates.Flexibility or adherence, rubber bullet are assigned to solidfied material as a result, The characteristic of property etc..
Second cross-linking polymerization is opening using the epoxy group of the epoxide of the hydroxyl of aromatic hydroxy compound Ring reaction.
In turn, it is anti-also to generate solidification caused by taking off the reacting of blocked isocyanate group and the epoxy group of epoxide It answers.
By these reaction formed solidfied material in gelatinous network, for mutually intrusion macromolecule it is netted (IPN: Interpenetrating Polymer Network) structure, contains a large amount of conducting fillers using resin combination preparation Heat conductive sheet when, the endurance quality that there is excellent flexibility, and excellent heat-resistant aging can be obtained etc..
(block urethane prepolymer)
The block urethane prepolymer contained in the resin combination is included in aliphatic diisocyanate chemical combination Object and two ends have in the reaction product of hydrogenated butadiene polymer class polyalcohol of hydroxyl, and the reaction product is had in end Isocyanate group pass through structure made of aromatic hydroxy compound block.The aliphatic two is come from the reaction product The structural unit of isocyanate compound is relative to 1 mole of structural unit from the hydrogenated butadiene polymer class polyalcohol 1.6-2.8 mole.
In addition, such as above-mentioned prepolymer, it is also difficult due to being difficult to the structure of the reaction product specifically for a kind of compound With by the structure of the prepolymer specifically for a kind of compound, therefore to use the describing mode of reactant to indicate.
<aliphatic diisocyanate compound>
Composition raw material, different with the reactant of hydrogenated butadiene polymer class polyalcohol as block urethane prepolymer Cyanate esters use aliphatic diisocyanate compound." aliphatic " in aliphatic diisocyanate compound, refers to Right and wrong " aromatic series ", the alkyl of substituent group can be straight-chain, branched or ring type.
As aliphatic diisocyanate compound, specifically, hexamethylene diisocyanate (HDI), two rings can be enumerated Hexyl methane diisocyanate (hydrogenation MDI), isophorone diisocyanate (IPDI) etc..They can be used alone, Two or more can be shared.In them, hydrogenation MDI or IPDI etc., steric hindrance is big, it is difficult to the reaction of isocyanates multimerization occurs, From the viewpoint of the easness of multimerization, particularly preferably with the HDI of more simple structure.
On the other hand, the aromatic series two of methyl diphenylene diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI) etc. is different Cyanate esters, the cohesive force using the carbamate groups of the block urethane prepolymer of their generations is strong, melting Temperature is high.Therefore, it is not cured reaction, maintains the state of prepolymer, the temperature model that can be mixed and mediate with conducting filler Enclose it is narrow, in kneading process operability it is poor.In turn, from the carbamate groups of aromatic diisocyanate compounds, with Carbamate groups from aliphatic diisocyanate compound is compared, and has what the decomposition temperature of carbamate groups was lower to incline To cannot get sufficient heat-resistant aging.
Structural unit from aliphatic diisocyanate compound in the reaction product, relative to from the poly- fourth of hydrogenation 1 mole of structural unit of dienes polyalcohol is 1.6-2.8 moles, preferably 1.7-2.7 moles, further preferably 1.8- 2.5 mole.
When structural unit from aliphatic diisocyanate compound is less than 1.6 moles, with block urethane The increase of the molecular weight of prepolymer, the operation when preparation of heat conductive sheet, when which is mediated as adhesive Property it is poor, uniformly mixing for resin combination and filler becomes difficult.On the other hand, aliphatic diisocyanate compound is more than At 2.8 moles, the increase of crosslink density caused by being reacted with the multimerization by isocyanates, in the solidification of resin combination It cannot get sufficient flexibility on object.
<hydrogenated butadiene polymer class polyalcohol>
It is reacted as the composition raw material of block urethane prepolymer, with the aliphatic diisocyanate compound The hydrogenated butadiene polymer class polyalcohol of object is that the double bond using butadiene as raw material, in the polyalcohol that two ends have hydroxyl is residual The compound that base is hydrogenated.The hydrogenated butadiene polymer class polyalcohol of high molecular weight is easy performance in the solidfied material of resin combination Flexibility.On the other hand, heat resistance can be improved in the hydrogenated butadiene polymer class polyalcohol of low molecular weight.
The number-average molecular weight of hydrogenated butadiene polymer class polyalcohol is come from the viewpoint of viscosity, heat resistance and acquirement easiness etc. It sees, preferably 800-5000.In addition, the number-average molecular weight in the present invention is the hydroxyl value according to JIS K1557-1:2007 measurement The value of calculating.
As hydrogenated butadiene polymer class polyalcohol, for instance, it may be preferable to GI-3000 (the equal molecule of number used as commercially available product Measure 3753 (goods catalogue expression values 3000)), GI-2000 (number-average molecular weight goods catalogue expression value 2000), GI-1000 (number Average molecular weight goods catalogue expression value 1000) (being Tso Tat Co., Ltd., Japan's system) etc..They can be used alone, Two or more can be shared.GI-3000 is particularly preferably in them.
Polyester polyol, the polyether alcohol, polycarbonate glycol used generally as polyurethanes raw material Deng, it is poorer than hydrogenated butadiene polymer class polyalcohol in terms of heat-resistant aging, humidity resistance and thermal shock resistance, thus not It is preferred that.
<aromatic hydroxy compound>
Aromatic hydroxy compound is the change that uses of block agent in the isocyanate group as the reaction product end Object is closed, with aromatic rings, and to constitute the aromatic compound that 1 or more hydrogen atom of the aromatic rings is optionally substituted by a hydroxyl group.Virtue Fragrant ring is preferably phenyl ring, in turn, the benzenediol that 2 hydrogen atoms of more preferably phenyl ring are optionally substituted by a hydroxyl group.Pass through aromatic hydroxyl The hydroxyl of compound is reacted with terminal isocyanate group, forms urethane bond, the terminal isocyanate of the reaction product Base is blocked.
In addition, in the block agent of isocyanate group, although there is aminated compounds, since it is anti-with epoxide Ying Xinggao, block urethane prepolymer become easy solidification, therefore not preferably.
As aromatic hydroxy compound, phenol, 1- cresols, 2- cresols, 3- cresols, 2,3- dimethyl can be specifically enumerated Phenol, 2,4- dimethyl phenol, 2,5- dimethyl phenol, 2,6- dimethyl phenol, 2,3,6- trimethyl phenol, 2,4,6- trimethyl phenol, 2,3, 5- trimethyl phenol, 3- isopropyl-phenol, 2- tert-butyl phenol, 3- tert-butyl phenol, 4- tert-butyl phenol, 2,4- di-tert-butylphenol, 2,5- bis- Tert-butyl phenol, 2,6- di-tert-butylphenol, 2,4,6- tri-tert-butyl phenol, 2- isopropyl -5- sylvan, 2,6- di-t-butyl -4- first Base phenol, 2- methoxyl group phenol, 3- methoxyl group phenol, 4- methoxyl group phenol, 2- ethyoxyl phenol, 3- ethyoxyl phenol, 4- ethyoxyl phenol, the third oxygen of 2- Base phenol, 3- propoxyl group phenol, 4- propoxyl group phenol, 1,2- benzenediol, 1,3- benzenediol (resorcinol), 1,4- benzenediol, 1,3,5- Benzenetriol, 4- tert-butyl catechol etc..They can be used alone, and can also share two or more.
In them, particularly preferably resorcinol.Resorcinol due to by isocyanate group it is blocked after carry out deintercalation section The temperature of change is 120 DEG C or so, relatively low, by reacting for isocyanate group and the epoxy group of epoxide, makes resin group When closing object solidification, can easily it take off blocked.
(epoxide)
The epoxide that the present invention uses, for the epoxide with 2-6 epoxy group, preferably 2-5 is a, and flat It is 2.5 or more.When epoxy group is 1, it is difficult to form gelatinous network by the solidification of resin combination.Another party Face, when epoxy group is 7 or more, it is difficult to form the appropriate gelatinous network with flexibility.
In addition, the epoxy group of the epoxide is relative to 1 mole of hydroxyl of the aromatic hydroxy compound 0.9-2.5 moles, preferably 0.9-2.2 moles, more preferably 1.0-2.0 moles, further preferably 1.0-1.2 moles.Ring When oxygroup is less than 0.9 mole, there is the tendency of heat-resistant aging variation.When on the other hand, more than 2.5 moles, resin combination Solidfied material to become flexibility bad.
The epoxide is preferably more in order to pass through the appropriate gelatinous network that is formed by curing of resin combination Function and structure is small-sized.From the point of view of the viewpoint, preferably molecular weight is less than 600 and epoxide equivalent is less than 200g/eq.Molecular weight is more Preferably 200-500, further preferably 300-450.
In addition, the compatibility or heat-resistant aging of other reactants from resin combination, humidity resistance and heat-resisting , it is preferable to use the compound with glycidyl group amine type ring oxygroup from the viewpoint of impact.Specifically, four shrinks can be enumerated Glyceryl diaminodiphenyl-methane, isocyanuric acid three-glycidyl ester etc..They can be used alone, and can also share 2 Kind or more.In them, particularly preferably four glycidyl group diaminodiphenyl-methane.
(curing catalysts)
Curing catalysts in the resin combination, be carry out the block of the reaction product isocyanate group it is de- It is blocked, promote the reaction of isocyanates multimerization, while promoting the epoxy group and aromatic hydroxy compound of epoxide The curing catalysts of the reaction of phenolic hydroxyl group.
As the curing catalysts, it is preferable to use quaternary ammonium salt, more preferably uses tetraalkylammonium salt.
Specifically, 2 ethyl hexanoic acid tetramethyl ammonium, 2 ethyl hexanoic acid tetraethyl ammonium salt, 2 ethyl hexanoic acid ethyl can be enumerated Leptodactyline, 2 ethyl hexanoic acid triethyl methyl ammonium salt, formic acid tetramethyl ammonium, formic acid tetraethyl ammonium salt, formic acid ethyl three Methyl ammonium salt, formic acid triethyl methyl ammonium salt, tetramethyl-ammonium phenolate, tetraethyl ammonium phenolate, ethyl trimethyl ammonium phenolate, Triethylmethylammonium phenolate etc..They can be used alone, and can also share two or more.In them, particularly preferably 2 ethyl hexanoic acid triethyl methyl ammonium salt.
The additive amount of curing catalysts, it is excellent relative to the total amount of block urethane prepolymer and epoxide It is selected as 0.1-1 mass %, more preferably 0.2-0.9 mass %, further preferably 0.3-0.6 mass %.
(additive)
It, can in addition to block urethane prepolymer, epoxide and curing catalysts in the resin combination Solidfied material according to the resin combination uses purpose or required characteristic, addition fire retardant, plasticizer, antioxidant etc. Additive.These additives are preferably the additive for having compatibility with the other compositions in resin combination.Each additive It can arbitrarily add, can be used alone as needed, two or more can also be shared.
As fire retardant, such as phosphazene compound, condensed phosphoric acid esters can be enumerated etc..Relative to block urethane pre-polymerization The total amount of object and epoxide, the additive amount of fire retardant is preferably 1-20 mass %, more preferably 1-15 mass %, into one Step is preferably 3-12 mass %.
As plasticizer, such as the plasticizer that xylene resin, atoleine, esters can be enumerated etc..
As antioxidant, such as the antioxidant that Hinered phenols can be enumerated etc..
Each additive amount of plasticizer or antioxidant etc., relative to block urethane prepolymer and epoxide Total amount, preferably 0.5-10 mass %, more preferably 0.7-8 mass %, further preferably 0.8-5 mass %.
In turn, in resin combination, in addition to the solvents contain the block urethane prepolymer and epoxidation in ingredient The total amount for closing object, from the viewpoint of the solidfied material of resin combination can be made to play good characteristic, preferably 75-100 matter Measure %, more preferably 80-100 mass %, further preferably 85-100 mass %.
[preparation method of resin combination]
Resin combination of the invention, there is no particular limitation for preparation method, can preparation method according to the present invention it is suitable Locality preparation.
The preparation method of resin combination of the invention, via following steps: making the aliphatic diisocyanate chemical combination Object and the hydrogenated butadiene polymer class polyalcohol, react in the presence of urethanation catalyst, obtain end with different The process (1) of the reaction product of cyanic acid ester group, adds the aromatic hydroxy compound in the reaction product, carries out The blocked reaction of isocyanate group obtains the process (2) of the block urethane prepolymer, and in the block ammonia In carbamate prepolymer, the epoxide and curing catalysts are at least blended, the process for obtaining the resin combination (3)。
(process (1))
In process (1), make aliphatic diisocyanate compound and hydrogenated butadiene polymer class polyalcohol, in carbamic acid It is reacted in the presence of esterification catalyst, obtains the reaction product that end has isocyanate group.
<urethanation catalyst>
Reaction product obtained in process (1) is the isocyanate group and hydrogenation by aliphatic diisocyanate compound The hydroxyl of two end of polybutadiene polyalcohol, formed urethane bond urethane reaction and generate.In this way Urethane reaction, in order to promote to react, it is preferable to use urethanation catalyst carry out.
Carry out urethane reaction in order not to use urethanation catalyst, it is necessary to be heated to 100 DEG C More than, at this high temperature, aliphatic diisocyanate compound becomes easy volatilization, and reaction system is easy to become uneven It is even, therefore not preferably.
There is no particular limitation for urethanation catalyst, such as can enumerate 1,8- diazabicyclo (5.4.0) 11 Carbene -7 (DBU), 1,5- diazabicyclo [4.3.0] nonene -5 (DBN) etc..They can be used alone, and can also share Two or more., it is preferable to use DBU in them.
The additive amount of urethanation catalyst, as long as the amount of urethane reaction, phase can be sufficiently promoted For total matter of aliphatic diisocyanate compound, hydrogenated butadiene polymer class polyalcohol and urethanation catalyst Amount, preferably 0.01-0.5 mass %, more preferably 0.01-0.2 mass %, further preferably 0.02-0.1 mass %.
(process (2))
In process (2), aromatic hydroxy compound is added in the reaction product obtained in the process (1), is carried out The blocked reaction of isocyanate group, obtains block urethane prepolymer.
The additive amount of aromatic hydroxy compound, from the viscosity rising and the resin combination for inhibiting resin combination It, should relative to 1 mole of isocyanate group of the aliphatic diisocyanate compound from the point of view of the viewpoints such as the flexibility of solidfied material The hydroxyl of aromatic hydroxy compound is preferably the amount for becoming 0.9-1.1 moles, more preferably 1.0 moles, as same amount.
<solvent>
By the blocked reaction of aromatic hydroxy compound, with the rising of viscosity.In addition, aromatic hydroxy compound After melting more than its fusing point, start blocked reaction, however due at this high temperature, can also occur as reversible reaction Take off blocked reaction so that it is blocked reaction be difficult to complete.
Therefore, in order to effectively complete blocked reaction, reaction temperature is preferably made to be reduced to 80-60 DEG C, preferably from about 70 DEG C, and diluted reactant using suitable solvent, reduce the viscosity of reaction system.
As solvent, from the viewpoint of the dissolubility of reactant etc., such as toluene, tetrahydrofuran (THF) can be enumerated etc..They It can be used alone, two or more can also be shared.In them, from the viewpoint of volatility or agent of low hygroscopicity etc., preferably Use toluene.
In addition, when preparing heat conductive sheet using obtained resin combination, in order to ensure mixed conducting filler Packing character, dispersibility, it is preferable to use such as THF equal solvents to dilute and be modulated into solution for block polyester-urethane prepolymer.
The concentration of block polyester-urethane prepolymer solution at this time, is filled out from thermal conductivity when ensuring to prepare heat conductive sheet From the viewpoint of Packing character, dispersibility and efficient activity of preparation of material etc., preferably 20-60 mass %, more preferably 30-50 matter Measure %, further preferably 35-45 mass %.
(process (3))
In process (3), in the block urethane prepolymer obtained in the process (2), epoxy is at least blended Compound and curing catalysts, obtain resin combination.
Resin combination preferably blended in block urethane prepolymer epoxide and curing catalysts it Afterwards, the resin combination equably mixed.As long as mixed method can make admixture in resin combination equably dissolve, disperse i.e. Can, there is no particular limitation.For example, admixture can be contained in closed container, then each container vibration is mixed, separately Outside, the admixture accommodated in container can also be stirred by stirring blade and is mixed.
In the resin combination, in addition to block urethane prepolymer, epoxide and curing catalysts, Fire retardant, plasticizer, antioxidant can be added according to the solidfied material of the resin combination using purpose or required characteristic Deng such as above-mentioned additive.
[thermal conductivity soft sheet material]
Thermal conductivity soft sheet material of the invention, for the resin combination comprising aforementioned present invention and thermal conductivity inorganic filler The resin sheet that blend compositions are formed by curing.Also, it is characterized by the basis of the c-type hardness test of JIS K7312:1996 The hardness determined is 95 thermal conductivity soft sheet materials below.
Resin combination of the invention is used as the heat conductive sheet of adhesive, is the thermal conductivity with excellent flexibility Soft sheet material.As long as it may be said that the hardness is 95 hereinafter, the flexibility that heat conductive sheet uses can be suitable as by having.
The hardness, specifically, using Asker c-type hardometer, according to the value for the method measurement that following embodiments are recorded.
In turn, heat conductive sheet of the invention, there is no particular limitation for usage mode, can be with previous heat conductive sheet Usage mode equally uses.
(thermal conductivity inorganic filler)
In thermal conductivity soft sheet material of the invention, use inorganic filler as conducting filler.It is inorganic as thermal conductivity Filler, from the viewpoint of insulating properties, such as can enumerate magnesia, aluminium oxide, boron nitride, aluminium nitride, magnesium hydroxide, aluminium hydroxide, Silica etc..They can be used alone, and can also share two or more.In addition, in the range of not influencing insulating properties, Aluminium powder, carbon black, black lead powder etc. can be blended.There is no particular limitation for the shape of thermal conductivity inorganic filler, for example, can enumerate broken shape, Spherical, plate etc..
In view of the balance of performance and cost, the mixing of preferably broken magnesia, spherical magnesia and ball-aluminium oxide Object, the mixture of spherical magnesia and the different 2 kinds of ball-aluminium oxides of partial size or broken magnesia and broken aluminium nitride it is mixed Close object etc..At this moment the mixing ratio in mixture, it is contemplated that compatibility and resin group with the resin combination as adhesive Close the dispersion flows or viscosity, in turn when object mixing, flammability of thermal conductivity soft sheet material etc. and be suitably determined.
The partial size of thermal conductivity inorganic filler does not influence the filling to the resin combination as adhesive, dispersion preferably Property, and the degree of the flexibility of thermal conductivity soft sheet material is not influenced, specifically, average grain diameter is preferably 0.1-150 μm, more excellent It is selected as 0.5-100 μm, further preferably 1-80 μm.In turn, the average grain diameter of the thermal conductivity inorganic filler in the present invention, is logical Cross partial size when cumulative volume 50% in the size distribution that laser diffraction formula particle size distribution device acquires.
The thermal conductivity inorganic filler, from improve with from the viewpoint of compatibility as the resin combination of adhesive, Preferably it is surface-treated with coupling agent.As coupling agent, and specifically, it is preferable to use aluminium chelate compound.Wherein, particularly preferably Alkyl acetoacetate aluminium diisopropanol compound.
Aluminium chelate compound, relative to total quality of thermal conductivity inorganic filler, preferably addition 0.1-5 mass %, more preferably For 0.3-2 mass %, further preferably 0.5-1.5 mass %.
From the viewpoint of effectively improving the compatibility with resin combination, it is surface-treated preferably by making in THF After thermal conductivity inorganic filler and aluminium chelate compound dispersion, THF is evaporated, makes it dry and carries out.
[preparation method of thermal conductivity soft sheet material]
Thermal conductivity soft sheet material of the invention, there is no particular limitation for preparation method, can preparation side according to the present invention Method is suitably prepared.
The preparation method of thermal conductivity soft sheet material of the invention, via following steps: by the resin combination at least with The thermal conductivity inorganic filler mixing, modulates the process (4) of the blend compositions, the blend compositions is mediated, calendering, The process (5) of uncured presoma is obtained, and by the way that the presoma pressurizes at 120-250 DEG C, keeps it solid Change, obtains the process (6) of the thermal conductivity soft sheet material.
Preparation method according to the present invention, in process (6) when pressurized, heated, due to can be in the hybrid combining of uniform state Start to carry out the curing reaction of resin combination in object, operability when preparation is excellent, can be readily derived uniform thermal conductivity Soft sheet material.
(process (4))
In process (4), resin combination is at least mixed with thermal conductivity inorganic filler, modulates blend compositions.
The resin combination is mixed with the adhesive as thermal conductivity inorganic filler, such as above-mentioned, can also be suitable for adding resistance The additive of agent, plasticizer, antioxidant etc. is fired, in addition, in order to be easy mixing, it is possible to use solvent dilution.
<blended amount>
The blend ratio of resin combination and thermal conductivity inorganic filler, there is no particular limitation, can be according to desired thermal conductivity Can or flexibility etc. and appropriate adjustment.The blended amount of resin combination, with total quality of thermal conductivity inorganic filler be 100 matter In the case where measuring part, preferably relative to this 5-25 mass parts, more preferably 7-20 mass parts, further preferably 10-15 Mass parts.
<mixed method>
There is no particular limitation for resin combination and the mixed method of thermal conductivity inorganic filler.By resin combination with molten Dilution agent and in use, for example, can by used simultaneously with thermal conductivity inorganic filler rotation-revolution mixing machine etc. blender or After the mixing such as dispersion machine, solvent is removed and evaporating or drying, obtains blend compositions.In addition, without using solvent In the case of, it can be by with monolith state, using the muller of three-roll grinder etc., blending resin composition and thermal conductivity is inorganic fills out Material, obtains blend compositions.
(process (5))
In process (5), blend compositions obtained in the process (4) is mediated, calendering, obtain uncured forerunner Body.
It mediates and rolls, the laminater such as hot spreader bar can be used and carry out.At 90 DEG C of temperature below into Row is so that blend compositions can maintain uncured state.Additionally, it is preferred that changing the pressure of pressurization, while repeating so that mixed Polymeric composition becomes uniform state.
When calendering, from the viewpoint of preventing presoma from adhering to the press rolled, such as polytetrafluoro can also be used Fluorine resin sheet material of ethylene (PTFE) etc. etc. and carry out.
In addition, uniform thermal conductivity soft sheet material, presoma preferably carry out at deaeration before process (6) in order to obtain Reason.Deaeration processing is preferably for example heated in the temperature lower than 150 DEG C, carries out vacuum defoamation with about 2-10 minutes short time.
There is no particular limitation for the shape of presoma, however is shaped from process (6) with sheet, in addition, from being easy From the viewpoint of deaeration, preferably become tabular.
(process (6))
In process (6), by being carried out at 120-250 DEG C by uncured presoma obtained in the process (5) Pressurization makes its solidification, obtains the thermal conductivity soft sheet material.By being heated at 120-250 DEG C in this process, start into The curing reaction of row resin combination obtains the homogeneous sheet forming body being made of the solidified body of blend compositions.
Pressurized, heated can be carried out by usually used hot press, thus can be by sheet forming.At this point, from presoma is prevented From the viewpoint of the adhesion of hot press, with the calendering the case where in the same manner as, the fluorine resin sheet material of PTFE etc. can also be used Deng progress.
From the curing reaction for starting resin combination, and moderately from the viewpoint of progress, heating temperature is preferably 120- 250 DEG C, more preferably 170-230 DEG C, further preferably 185-200 DEG C.
The suitable setting according to the thickness of desired sheet forming body or the amount of presoma etc. of moulding pressure and pressing time. Usually 0.1-5MPa or so, 5-60 minutes or so.
[radiator structure]
Radiator structure of the invention is with heater and radiator clamping such as above-mentioned thermal conductivity soft sheet material of the invention Structure.By the way that thermal conductivity soft sheet material of the invention to be held between heater and radiator, fever can be effectively performed The heat dissipation of body.In addition, thermal conductivity soft sheet material of the invention is due to not siliceous class material, radiator structure according to the present invention, no It can lead to the problem of since the volatilization of low molecular weight polyorganosiloxane causes the contact obstacle or poor flow etc. of electric device.
(heater radiator)
There is no particular limitation for heater, can enumerate in Electrical connections, with 150 DEG C of fevers below when use Electronic component, such as LED or CPU, power supply IC etc. can be enumerated as applicable object.
Also there is no particular limitation for radiator, can enumerate in Electrical connections, usually as dissipating for the heater The radiator that hot body uses, such as heat sink or metal framework, heat sink etc. can be enumerated as applicable object.
In addition, there is no particular limitation for the clamp method and method of clamping of thermal conductivity soft sheet material, can with it is previous thermally conductive Property sheet material the same manner operation.
[embodiment]
Hereinafter, the present invention is described in detail by embodiment, however the present invention is not limited by this.
[preparation of block urethane prepolymer (A)]
According to method shown in following preparation examples, block urethane prepolymer (A1)-(A5) is prepared.In each block In the preparation of carbamate prepolymer, the raw material used is as follows.
Aliphatic diisocyanate compound (a1)
Hexamethylene diisocyanate；" Desmodur H " firmly changes Covestro Urethane Co. Ltd. system
Polyalcohol (a2)
(a2-1) hydrogenated butadiene polymer class polyalcohol；" GI-3000 ", Tso Tat Co., Ltd., Japan's system, molecular weight 3753, hydroxyl Radix 29.9KOHmg/g
(a2-2) polyester polyol: 3- methyl-1, the adipate ester of 5- pentanediol；" P3010 ", Co., Ltd. Kuraray system, molecular weight 3082, hydroxyl value 36.4KOHmg/g
(a2-3) polyether alcohol: the ring-opening polymerization polymer (supposition) of 3- methyltetrahydrofuran and THF；" PTG-L3000 ", Baotugu Chemical Industrial Co., Ltd's system；Molecular weight 2992, hydroxyl value 37.2KOHmg/g
Isocyanate group block agent (a3)
(a3-1) resorcinol；Reagent is superfine；Wako Pure Chemicals Co., Ltd. system
(a3-2) ethylene diamine: reagent is superfine；Wako Pure Chemicals Co., Ltd. system
Urethanation catalyst
1,8- diazabicyclo [5.4.0] endecatylene -7 (DBU), San-Apro Co. Ltd. system
Solvent
Toluene；Reagent is superfine, and Wako Pure Chemicals Co., Ltd. system has carried out dehydration with 4A molecular sieve
THF；Reagent is superfine, Wako Pure Chemicals Co., Ltd. system
The preparation of (preparation example 1) block urethane prepolymer (A1)
In 300ml detachable flask, aliphatic diisocyanate compound (a1) 3.26g and polyalcohol (a2- is added 1) 34.59g, installation stirring blade, stirring motor, snakelike double helix condenser pipe and nitrogen ingress pipe.To in flask with per minute The flow of 200ml carries out nitrogen purging, which is immersed in 75 DEG C of oil bath, with 30rpm stirring 5 minutes, is prepared After mixing, it will be adjusted to 150rpm in rotation number, reacted.
After five minutes, confirm that the content in flask is full and uniform, addition DBU 0.02g is catalyzed as urethane Agent.After 3 hours, for content, when measuring infrared absorption spectrum (IR spectrum), the 3300cm from hydroxyl is confirmed-1Signal It disappears.
The temperature of oil bath is warming up to 125 DEG C, after flask sufficiently heats, puts into the isocyanate group block agent of 2.13g (a3-1), after with 400rpm stirring 3 minutes, the temperature of oil bath is reduced to 110 DEG C, continues to stir with 50rpm.Confirm in flask Temperature be 110 DEG C after, add toluene 22.16g.Mixing speed is slowly risen, 150rpm is fixed on, the temperature of oil bath is dropped Down to 70 DEG C, react 3 hours.For content, the 2270cm from isocyanate group is confirmed with IR spectrum-1The disappearance of signal.
It lets cool to room temperature, adds THF 37.84g, stirring becomes uniformly, it is pre- to obtain block urethane to content Polymers (A1) solution 100.00g (40.0 mass % (calculated value) of concentration).
(preparation example 2-7) block urethane prepolymer (A2)-(A7) preparation
In preparation example 1, be changed to raw material proportioning shown in the preparation example 2-7 of following table 1, in addition to this, with preparation 1 the same manner of example obtains block urethane prepolymer (A2)-(A7) solution.
The preparation of (preparation example 8) block urethane prepolymer (A8)
In 500ml detachable flask, aliphatic diisocyanate compound (a1) 3.10g and polyalcohol (a2- is added 1) 34.59g, installation stirring blade, stirring motor, snakelike double helix condenser pipe and nitrogen ingress pipe.To in flask with per minute The flow of 200ml carries out nitrogen purging, which is immersed in 75 DEG C of oil bath, and 30rpm is stirred 5 minutes, and it is mixed to carry out preparation After conjunction, reacted 150rpm is adjusted in rotation number.
After five minutes, confirm that the content in flask is full and uniform, addition DBU 0.02g is catalyzed as urethane Agent.After 3 hours, when measuring infrared absorption spectrum (IR spectrum) for content, the 3300cm from hydroxyl is confirmed-1Signal disappears It loses.Wherein, toluene 339.39g is put into, 10.0 mass % toluene solutions are obtained.
In 2000ml detachable flask, the 5 mass %THF solution of the agent of isocyanate group block (a3-2) are put into 553g.It is stirred nitrogen purging is carried out in flask after being cooled to 5 DEG C in sink with 300rpm, while by rouge obtained above The toluene solution of the reaction product of fat (cyclo) aliphatic diisocyanates compound (a1) and polyalcohol (a2-1) is small with 3 by dropping funel When instill.It instills after ending, the temperature of sink is risen to 40 DEG C, and with 150rpm stirring 1 hour, reacted.For content Object confirms the 2270cm from isocyanate group by IR spectrum-1The disappearance of signal.
By in the content solvent and residual isocyanate base block agent (a3-2: ethylenediamine), use rotary evaporator It evaporates, in turn, vacuum drying treatment 3 days at 160 DEG C obtain the refined substance of block urethane prepolymer.
Obtained block urethane prepolymer 40g is added in 300ml detachable flask.In the flask, throw The mixed solvent (total 60.00g) for entering toluene 22.22g and THF 37.78g, in a nitrogen atmosphere, is stirred on one side with 150rpm, It flows back 5 hours in 90 DEG C of oil bath on one side, obtains block urethane prepolymer (A8) solution (40.0 mass % of concentration).
[table 1]
Table 1
[preparation of resin combination]
According to method shown in following embodiment and comparative example, various resin combinations are prepared.In each resin combination Preparation used in raw material it is as follows.
Block urethane prepolymer (A)
Prepared block urethane prepolymer (A1)-(A8) in above-mentioned preparation example 1-8
Epoxide (B)
Four glycidyl group diaminodiphenyl-methane；" Epototo YH-434L ", Nippon Steel & Sumitomo Metal Corporation System, epoxide equivalent 118.1g/eq
Curing catalysts (C)
2 ethyl hexanoic acid triethyl methyl ammonium salt；" U-CAT18X ", San-Apro Co. Ltd. system
Additive
Antioxidant: bis- [2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) the propionyloxy] -1,1- dimethyl of 3,9- Ethyl] -2,4,8,10- four oxaspiro [5.5] hendecane；" Sumilizer (registered trademark) GA-80 ", Sumitomo Chemical strain formula meeting Society's system
Fire retardant: phosphazene flame retardant；" SPB-100 ", Otsuka Kagaku K.K.'s system
Plasticizer: xylene resin " Nikanol (registered trademark) LR ", Fudow Co. Ltd. system
·THF
Reagent is superfine, Wako Pure Chemicals Co., Ltd. system
(embodiment 1)
In 250ml polyethylene wide-mouth bottle, block urethane prepolymer (A1) solution 100.00g, epoxy is added 50.5 mass %THF solution 9.53g, the 10.0 mass %THF solution 2.24g of curing catalysts (C), conduct of compound (B) Antioxidant 0.45g, fire retardant 4.48g and the plasticizer 1.34g of additive shake mixing, it is (dense to obtain resin composition solution Spend 43.46 mass %).
(embodiment 2-7, comparative example 1-7)
In embodiment 1, be changed to raw material proportioning shown in the embodiment 2-7 and comparative example 1-7 of following table 2, except this with Outside, in a manner of similarly to Example 1, each resin composition solution is obtained.
In addition, the resin composition solution of comparative example 7, solution viscosity rises in modulation, it is difficult to be used for sheet material at The preparation of body.Be considered terminal amino group due to isocyanate group block agent (a3-2) and epoxide (B) reacts production The reason that raw polymerization reaction is exceedingly fast.
[table 2]
[modulation of thermal conductivity inorganic filler]
(modulation example 1) thermal conductivity inorganic filler (F1)
In 100ml polyethylene wide-mouth bottle, broken magnesia (60 μm of average grain diameter) 44.75g, spherical magnesia is added (20 μm of average grain diameter) 21.05g and ball-aluminium oxide (7 μm of average grain diameter) 10.40g shakes mixing.
Wherein, alkyl acetoacetate aluminium diisopropanol compound 0.87g and THF 22.86g is added, mixing is shaken.
Then, using rotation-revolution mixing machine, with 2000rpm stirring 2 minutes, next, by supersonic cleaning machine into 30 minutes decentralized processings of row, then with rotation-revolution mixing machine, with 2000rpm stirring 2 minutes.Then, by content with 60 DEG C of temperature Air-dry it is dry, then with 70 DEG C carry out 5 hours be dried in vacuo, remove THF, obtain thermal conductivity inorganic filler (F1).
(modulation example 2) thermal conductivity inorganic filler (F2)
In 100ml polyethylene wide-mouth bottle, spherical shape magnesia (20 μm of average grain diameter) 43.47g, ball-aluminium oxide is added (5 μm of average grain diameter) 22.60g and ball-aluminium oxide (3 μm of average grain diameter) 10.13g shakes mixing.
Wherein, alkyl acetoacetate aluminium diisopropanol compound 0.86g and THF 22.86g is added, mixing is shaken.
Subsequent processing and modulation example 1 are same, obtain thermal conductivity inorganic filler (F2).
(modulation example 3) thermal conductivity inorganic filler (F3)
In 100ml polyethylene wide-mouth bottle, broken magnesia (60 μm of average grain diameter) 54.94g and broken nitridation is added Aluminium (13 μm of average grain diameter) 21.26g shakes mixing.
Wherein, alkyl acetoacetate aluminium diisopropanol compound 0.87g and THF 22.86g is added, mixing is shaken.
Subsequent processing and modulation example 1 are same, obtain thermal conductivity inorganic filler (F3).
[preparation of sheet forming body (thermal conductivity soft sheet material)]
(embodiment 8)
In 50ml spiral phial, the resin of the thermal conductivity inorganic filler (F1) of 10.00g and the embodiment 1 of 2.84g is added Composition solution, using rotation-revolution mixing machine, with 2000rpm stirring 2 minutes, next, carrying out 30 with supersonic cleaning machine Minute decentralized processing, then blend compositions were modulated with 2000rpm stirring 2 minutes with rotation-revolution mixing machine.By this hybrid combining Object takes out into stainless steel cylinder, cylinder is placed on after heating 1 hour on 80 DEG C of hot plate, and it is dry that 30 minutes vacuum are carried out at 90 DEG C It is dry, remove solvent volatilization.
By the blend compositions of the removing solvent of about 11g, using 90 DEG C of hot spreader bar, in 200 μm of sheet of PTFE of thickness It holds the blocky blend compositions into size about 30mm between material under the arm, by pressurizeing repeatedly from the outside of upper and lower PTFE sheet, is pinched It closes, calendering.It mediates and rolls with pressure 1.0kN pressurization 10 times, subsequent 10 times, each increase 0.1kN's every 1 time from 1.1kN Pressure is pressurizeed, and it is 1 time every while folded and amounted to 20 times repeatedly, obtain that final thickness is about 700 μm, diameter is The flat uncured presoma of about 80mm.Then, the PTFE sheet for stripping the presoma top side carries out 3 at 140 DEG C Minute vacuum defoamation.
It holds deaeration presoma and 2 500 μm of thickness of liner between 200 μm of thickness of PTFE sheet under the arm, with small-sized pressure Contracting forming machine is at 185 DEG C, with 1.2kN through 30 seconds, 5kN through 2 minutes, 10kN through 12 points 30 seconds, carry out pressurized, heated.In turn, 15 minutes pressurized, heateds are carried out with 1.2kN, obtaining final thickness is about 500-650 μm, the sheet forming body that diameter is about 100mm Thermal conductivity soft sheet material.
(embodiment 9-14, comparative example 8-13)
In embodiment 8, it is changed to resin combination shown in the embodiment 9-14 and comparative example 8-13 of following Table 3 and leads Hot inorganic filler in a manner of similarly to Example 8, obtains each sheet forming body in addition to this.
[evaluation of measuring]
Each sheet forming body obtained in above-described embodiment and comparative example carries out various evaluation of measuring below.It will These measure and evaluate result and are shown in table 3.
(ductility)
Ductility when kneading is the index that whether curing reaction carries out in the process for obtaining presoma.
The resin combination that curing reaction carries out in the process for obtaining presoma, the poor ductility of presoma, thermal conductivity The formability of sheet material is poor.
Evaluation is to be carried out in the process for obtaining presoma with visually confirming.Determinating reference is as follows.
◎: being extensible to about 700 μm of thickness, presoma no cracking, and surface is uniform.
Zero: being extensible to about 800 μm of thickness, presoma no cracking, surface is uniform.
△: 900 μm or more of thickness can only be extended into, however presoma no cracking, surface are uniform.
×: presoma is cracked or surface is uneven, has convex-concave.
(average thickness)
About sheet forming body, by digital display thickness gauge (" SMD-540S2 ", Co., Ltd.'s Teclock system), any 5 Place's measurement thickness, using their average value as average thickness.
If average thickness is 500-700 μm, it is known as having excellent moldability.
(state on surface)
The state on the surface of sheet forming body is whether the reactant when curing reaction of resin combination starts remains suitable The index of the viscosity of degree.
At the beginning of curing reaction, in the case where reactant does not maintain appropriate viscosity, resin combination and thermal conductivity Inorganic filler becomes easy separation, it is difficult to obtain the sheet forming body of homogeneous.Especially at the edge of sheet forming body, occur empty Cave, or generate crack, it is difficult to it is used as heat conductive sheet.
Evaluation is the surface for obtained sheet forming body, is carried out with visually confirming.Determinating reference is as follows.
◎: without hole or crack, surface substantially uniformity.
Zero: though there are hole or crack within edge 3mm, however the surface of the part other than it is uniform.
△: though there are hole or crack within edge 10mm, however the surface of the part other than it is uniform.
×: also there are hole or crack from edge 10mm or more (near center portion).
(ash levels are poor)
In sheet forming body ash levels be unevenly thermal conductivity inorganic filler dispersibility index.Sheet forming body Center and the ash levels at edge difference it is big in the case where, the thermal conductivity of sheet forming body generates uneven.
Evaluation is by using showing differential thermal Libra (TG-DTA；" TG8120 ", Co., Ltd. Neo-Confucianism's system), by sheet forming body Center and edge each sample, be heated to 800 DEG C from room temperature with 10 DEG C/minute in air, measure weight reduction rates [%] and It carries out.The difference in center and the weight reduction rates at edge, as the ash levels difference both corresponded to value and determined.Determine Benchmark is as follows.
◎: the difference of weight reduction rates is less than 1%
Zero: the difference of weight reduction rates is 1% more than and less than 1.5%
△: the difference of weight reduction rates is 1.5% more than and less than 2%
×: the difference of weight reduction rates is 2% or more
(hardness)
The hardness of sheet forming body is the index of flexibility.
The value of the hardness measured on the basis of the c-type hardness test of JIS K7312:1996 is bigger to indicate harder, if 95 Hereinafter, can be described as heat conductive sheet with abundant flexibility.
Measurement is the lamination sample for becoming thickness 20mm or more (about 20mm) for sheet forming body, uses Asker c-type Hardometer (" Asker c-type durometer ", macromolecule gauge Co. Ltd. system) carries out.
In addition, comparative example 11 fails to measure due to really up to the mark, "-" is recorded as in table 3.
(viscosity)
The viscosity of sheet forming body is whether heat conductive sheet is easy hair between the heater and radiator being engaged with it The index of raw offset.
In the case where viscosity is low, the sticky limit of heater and radiator when the use of heat conductive sheet becomes not fill Point, it is difficult to play sufficient thermal conductivity.
Evaluation is carried out according to method as shown below.It is referred to as sticky good if being 1.5N or more according to the measured value of the method It is good.
At 25 DEG C of temperature, sheet forming body is placed on 150mm × 150mm × thickness 3mm aluminium sheet, places side on it Long 15mm rectangular aluminum thermal fin (side edge portions have wire handle).Use mechanical pull and push dynamometer (" FB- 20N ", Co., Ltd.'s Imada system), from cooling fin, with forcing for 20N, after being kept for 10 seconds, pull handle, measurement is pulled open Required power and carry out.
(thermal conductivity)
The product representation of the density of thermal conductivity sample, specific heat and thermal diffusivity.If thermal conductivity is 3.0W/ (mK) or more, Referred to as there is sufficient thermal conductivity.
Density, specific heat and thermal diffusivity are measured by method as shown below respectively.
<density>
Is measured by thickness and weight and is calculated for sheet forming body punching using the perforating press of the attached graver of diameter 9mm.
<thermal diffusivity>
It is evaluated by laser flash method.Determination condition is as follows.
Measurement device: " LFA447 Nano Flash (registered trademark) ", Netch society system
Sample: 10mm × 10mm
Sample holder: Nano Flash 10.0sq
Rating model: single layer
Measuring temperature: 25.0 ± 1.0 DEG C
The shooting number of every 1 measuring point: 3 times
Pulse width modified tone: in
Minute: 1000ms
The fitting of temperature rising curve and analytic modell analytical model: Cowan+pulse correction
<specific heat>
Use differential scanning calorimetry (DSC；" Thermo Plus DSC8230 ", Co. Ltd. system of science), with alpha-oxidation Aluminium is measured as standard substance.
(heat-resistant aging)
By by sheet forming body with gear type weatherometer (" TG-100 ", Suga testing machine Co. Ltd. system), 150 DEG C processing 1000 hours after thermal conductivity conservation rate and rubber-like elasticity domain ceiling temperature, evaluated.It is kept in thermal conductivity Rate is high, and rubber-like elasticity domain ceiling temperature is before treatment in rear unconverted situation, and referred to as heat-resistant aging is excellent.
<thermal conductivity conservation rate>
According to the thermal conductivity of the said determination method sample that acquires that treated, with its thermal conductivity relative to untreated sample Ratio, as thermal conductivity conservation rate.
<rubber-like elasticity domain ceiling temperature>
By measuring the dynamic elastic modulus ratio of sample before and after the processing, rubber-like elasticity domain ceiling temperature is acquired.Determination condition As follows.
Measurement device: hot mechanicalness analytical equipment (" TMA/SS6100 ", Seiko instrument Co. Ltd. system)
Frequency: 0.1Hz
Amplitude: 1.0mN
Temperature: 25 DEG C -350 DEG C
Heating rate: 10 DEG C/minute
Determinating reference is as follows.
Zero: rubber-like elasticity domain ceiling temperature is unchanged before and after the processing or reduces less than 5 DEG C
△: rubber-like elasticity domain ceiling temperature reduces by 5 DEG C more than and less than 20 DEG C before and after the processing
×: rubber-like elasticity domain ceiling temperature reduces by 20 DEG C or more before and after the processing
(humidity resistance)
By by sheet forming body with Constant Temperature and Humidity Chambers (" PH-2KT-E ", Espec Co. Ltd. system), with 80 DEG C, 95% Thermal conductivity conservation rate and rubber-like elasticity domain ceiling temperature after RH processing 1000 hours are evaluated.In thermal conductivity conservation rate Height, rubber-like elasticity domain ceiling temperature is before treatment in rear unconverted situation, and referred to as humidity resistance is excellent.
Thermal conductivity conservation rate and rubber-like elasticity domain ceiling temperature, the same manner is asked the case where to evaluate with heat-resistant aging ?.
(thermal shock resistance)
By by sheet forming body with thermal cycling test machine (" TSA-71S ", Espec Co. Ltd. system), with -30 DEG C~ It 100 DEG C, is recycled through 1 hour lifting temperature as 1, the thermal conductivity conservation rate and rubber after being reprocessed 1000 circulations Shape elastomeric domain ceiling temperature, is evaluated.It is high in thermal conductivity conservation rate, rubber-like elasticity domain ceiling temperature before treatment after without change In the case where change, referred to as thermal shock resistance is excellent.
Thermal conductivity conservation rate and rubber-like elasticity domain ceiling temperature, the same manner is asked the case where to evaluate with heat-resistant aging ?.
[table 3]
The result shown in the table 3 it is found that embodiment 8-14 sheet forming body, ductility when resin combination is mediated is excellent Good, the state on surface is also good, generally uniform, has abundant thermal conductivity, flexibility and adherence as heat conductive sheet.Separately Outside, indicate that heat resistance, humidity resistance and the thermal shock resistance of endurance quality are also excellent.

Claims (11)

1. a kind of resin combination comprising block urethane prepolymer, epoxide and curing catalysts,
The block urethane prepolymer is the hydrogenation for having hydroxyl in aliphatic diisocyanate compound and two ends In the reaction product of polybutadiene polyalcohol, the reaction product is passed through into aromatic series hydroxyl in the isocyanate group that end has Based compound block forms,
Structural unit from the aliphatic diisocyanate compound in the reaction product, relative to from the hydrogenation 1 mole of structural unit of polybutadiene polyalcohol is 1.6-2.8 moles,
The epoxide has 2-6 epoxy group, described relative to 1 mole of hydroxyl of the aromatic hydroxy compound Epoxy group is 0.9-2.5 moles.
2. resin combination according to claim 1, wherein the molecular weight of the epoxide is less than 600, and ring Oxygen equivalent is less than 200g/eq.
3. resin combination according to claim 1 or 2, wherein the number of the hydrogenated butadiene polymer class polyalcohol is divided equally Son amount is 800-5000.
4. resin combination described in any one of -3 according to claim 1, wherein between the aromatic hydroxy compound is Benzenediol.
5. resin combination described in any one of -4 according to claim 1, wherein the curing catalysts are quaternary ammonium salt.
6. a kind of preparation method of resin combination is the system of resin combination described in any one of claim 1-5 Preparation Method, this method include following process:
Make the aliphatic diisocyanate compound and the hydrogenation polybutadiene in the presence of urethanation catalyst Alkenes polyol reaction, the process for obtaining reaction product of the end with isocyanate group；
The aromatic hydroxy compound is added in the reaction product, carries out the blocked reaction of the isocyanate group, The process for obtaining the block urethane prepolymer；And
The epoxide and the curing catalysts are at least blended in the block urethane prepolymer, obtains institute The process for stating resin combination.
7. the preparation method of resin combination according to claim 6, wherein obtaining, the block urethane is pre- In the process of polymers, by the aromatic hydroxy compound with the isocyanic acid relative to the aliphatic diisocyanate compound The hydroxyl of 1 mole of aromatic hydroxy compound of ester group is that 0.9-1.1 moles of mode is added.
8. a kind of thermal conductivity soft sheet material is to make containing resin combination described in any one of claim 1-5 and lead Resin sheet made of the blend compositions solidification of hot inorganic filler,
Hardness according to the c-type determination of hardness test of JIS K 7312:1996 is 95 or less.
9. thermal conductivity soft sheet material according to claim 8, wherein the thermal conductivity inorganic filler is carried out with aluminium chelate compound Surface treatment.
10. a kind of preparation method of thermal conductivity soft sheet material is the system of thermal conductivity soft sheet material described in claim 8 or 9 Preparation Method, this method include following process:
The resin combination is at least mixed with the thermal conductivity inorganic filler, the process for modulating the blend compositions；
It mediates, roll the blend compositions, the process for obtaining uncured presoma；And
By the way that the presoma is pressurizeed at 120-250 DEG C and makes its solidification, the process for obtaining the thermal conductivity soft sheet material.
11. a kind of radiator structure is with thermal conductivity soft sheet material described in heater and radiator clamping claim 8 or 9.
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